阅读说明：本技术 一种测定水质、土壤或城市污泥中挥发酚和氰化物的方法 (Method for measuring volatile phenol and cyanide in water quality, soil or municipal sludge ) 是由 韩文红 李鹏飞 王珏纯 李岩 陈吉 杨燕旭 于 2020-07-21 设计创作，主要内容包括：本发明属于化学成分检测技术领域,公开了一种测定水质、土壤或城市污泥中挥发酚和氰化物的方法,所述测定水质、土壤或城市污泥中挥发酚和氰化物的方法包括：分别进行挥发酚溶液和氰化物溶液的配制；进行挥发酚和氰化物标准曲线浓度确定；进行土壤或是城市污泥的处理,制备待测样品；分别进行挥发酚和氰化物的测定、分析；分别进行挥发酚溶液和氰化物溶液的吸光度测定,并分别进行线性回归方程的获取。本发明的挥发酚和氰化物测定方法可以实现对水以及土壤、城市污泥等物质中挥发酚和氰化物含量的准确测定,避免其对人体造成的伤害；本发明的测定方法操作简单,检测的准确性更好；绘制标准曲线便于之后的检测。(The invention belongs to the technical field of chemical component detection, and discloses a method for measuring volatile phenol and cyanide in water quality, soil or municipal sludge, which comprises the following steps: respectively preparing volatile phenol solution and cyanide solution; carrying out concentration determination on volatile phenol and cyanide standard curves; treating soil or municipal sludge to prepare a sample to be detected; respectively measuring and analyzing volatile phenol and cyanide; and (4) respectively measuring the absorbance of the volatile phenol solution and the cyanide solution, and respectively obtaining a linear regression equation. The method for measuring the volatile phenol and the cyanide can accurately measure the content of the volatile phenol and the cyanide in water, soil, municipal sludge and other substances, and avoid the damage to human bodies; the determination method is simple to operate, and the detection accuracy is better; drawing a standard curve facilitates later detection.)

1. A method for measuring volatile phenols and cyanides in water quality, soil or municipal sludge is characterized by comprising the following steps:

step one, preparing a volatile phenol solution: mixing the volatile phenol standard solution with the concentration of 1000mg/L with a sodium hydroxide solution with the concentration of 0.025mol/L, and diluting the mixture into a volatile phenol solution with the concentration of 1 mg/L;

step two, preparing a cyanide solution: mixing a cyanide standard solution with the concentration of 50mg/L with a sodium hydroxide solution with the concentration of 0.025mol/L, and diluting the mixture into a cyanide solution with the concentration of 2 mg/L;

step three, determining the concentration of a volatile phenol standard curve: sucking the prepared volatile phenol solution into a constant volume bottle, and performing constant volume by using distilled water to obtain different standard curve concentrations of volatile phenol;

step four, determining the concentration of a cyanide standard curve: sucking the prepared cyanide solution into a constant volume bottle, and performing constant volume by using distilled water to obtain different standard curve concentrations of cyanide;

step five, treating water quality, soil or municipal sludge: taking a sample of water quality soil or municipal sludge to be detected; placing soil or municipal sludge in distilled water, uniformly stirring the soil or the municipal sludge by a stirring device, and placing the soil or the municipal sludge in an ultrasonic instrument for ultrasonic treatment to obtain a mixed solution;

step six, preparing a sample to be detected: filtering the mixed solution obtained in the fifth step by using a filter membrane, and filtering impurities and turbid substances in the mixed solution to obtain a sample to be detected;

and step seven, respectively measuring volatile phenol and cyanide: conveying a sample to be detected and a chemical reagent into a continuous flow injection analyzer with a volatile phenol and cyanide analysis module by using a pump, acidifying the sample to be detected by a distillation reagent, distilling out volatile phenol, collecting, and measuring the sample to be detected;

step eight, analyzing a sample to be detected: activating the flow injection analysis device, and setting the time relay to be in a mode of manually turning on and powering off after being powered on for 20-60 s; adjusting a base line, selecting a gain value after stabilization, then converting the analyzer into a sample introduction state, filling a sample introduction ring with a standard sample or a sample by driving of a first low-pressure pump, and then converting the analyzer into an analysis state to analyze a sample to be detected;

step nine, in the flow injection analysis process, manually turning on a power supply of the time relay, controlling the second electromagnetic valve to be communicated with the waste liquid container to input the reaction liquid output by the reactor into the waste liquid container, and simultaneously controlling an air inlet of the first electromagnetic valve to be communicated with the atmosphere to input air into the optical flow cell;

step ten, obtaining a linear curve: dividing a sample to be detected into two equal parts, putting the first part into a medium with the pH value of 10.0 +/-0.2, and carrying out online distillation to obtain a distillate;

step eleven, mixing distillate obtained by the first part of on-line distillation with continuously flowing 4-aminoantipyrine solution and potassium ferricyanide solution, carrying out oxidation color development to form yellow antipyrine dye, and carrying out colorimetric determination at the wavelength of 510nm by using a colorimeter;

step twelve, reacting the second part of samples with chloramine T under the condition that the pH value is less than 8 to form cyanogen chloride-CNCl, reacting the cyanogen chloride with an isonicotinic acid-barbituric acid reagent to form a violet blue dye, carrying out colorimetric determination by a colorimeter at the wavelength of 600nm, and respectively obtaining a linear regression equation.

2. The method for measuring the volatile phenols and cyanides in water quality, soil or municipal sludge according to claim 1, wherein in step three, the standard curve concentrations of the different volatile phenols are 0, 0.002, 0.004, 0.008, 0.012, 0.020, 0.030 and 0.040, respectively.

3. The method according to claim 1, wherein in the fourth step, the standard curve concentrations of different cyanides are 0, 0.004, 0.008, 0.016, 0.024, 0.032, 0.040 and 0.060 respectively.

4. The method for measuring the volatile phenols and cyanides in water quality, soil or municipal sludge according to claim 1, wherein in step five, the ultrasonic treatment is carried out under the following conditions: the ultrasonic frequency is 1.7-2.4 MHz, and the ultrasonic time is 10-20 min.

5. The method for measuring the volatile phenols and cyanides in water quality, soil or municipal sludge according to claim 1, wherein in step six, the method for filtering the mixed solution comprises: and filtering the mixed solution by using a filter membrane with the thickness of 0.30-0.50 nm for 2-3 times.

6. The method for measuring the volatile phenols and cyanides in the water quality, the soil or the municipal sludge according to claim 1, wherein in the seventh step, the method for measuring the sample to be measured comprises the following steps:

(1) sending a sample to be tested into a continuous flow injection analyzer with a volatile phenol and cyanide analysis module;

(2) sequentially opening a circulating water cooling machine, a flow injection analyzer host and a sample injector;

(3) opening the peristaltic pump when the temperature of the distiller rises to 100 ℃; and (6) carrying out the determination of the sample to be detected.

7. The method for measuring volatile phenols and cyanides in water, soil or municipal sludge according to claim 1, wherein in step seven, when the volatile phenols and cyanides are measured separately, the volatile phenols and cyanides are measured separately 8 to 10 times.

8. The method for measuring volatile phenols and cyanides in water quality, soil or municipal sludge according to claim 1, wherein in step seven, the distillation reagent is a phosphoric acid solution and is prepared by the following method: 30ml of phosphoric acid with the density of 1.65g/ml is added into 50ml of distilled water, and the volume is increased to 200ml by adding the distilled water.

9. The method for measuring volatile phenols and cyanides in water quality, soil or municipal sludge according to claim 1, wherein in step eight, the method for analyzing the sample to be measured is a flow injection analysis method.

10. The method for determining volatile phenols and cyanides in water quality, soil or municipal sludge according to claim 1, wherein in step twelve, the linear regression equation is obtained by:

calculating the content of the sample according to the peak area of the sample to be measured and a standard curve, wherein the calculation formula is as follows:

Y＝a+bX；

wherein, Y is the peak area of sample determination; x is the content of the sample and the unit is mu g/L; a is a standard curve intercept; b is the standard curve slope.

Technical Field

The invention belongs to the technical field of chemical component detection, and particularly relates to a method for measuring volatile phenol and cyanide in water quality, soil or municipal sludge.

Background

At present, phenols belong to high-toxicity substances and are mainly derived from industrial sewage, and long-term drinking of water polluted by phenols can cause headache, eruption, pruritus, anemia and various nervous system symptoms. Cyanide belongs to a highly toxic substance, and the toxicity to human bodies is mainly that the cyanide is combined with ferricytochrome oxidase to generate cyaniding ferricytochrome oxidase and lose the effect of transferring oxygen, so that hypoxia asphyxia is caused. The determination of volatile phenol and cyanide is a basic item of surface water environmental quality standard and domestic sewage and industrial wastewater comprehensive emission standard in the national environmental monitoring field, the volatile phenol and cyanide are also basic items of soil and municipal sludge pollutant detection, and the detection items have large sample amount and high working strength in daily monitoring work in the environmental protection field. The existing method for measuring volatile phenol and cyanide in water quality, soil or municipal sludge is complex and long in time consumption, and is extremely easy to cause harm to the health of measuring personnel.

Through the above analysis, the problems and defects of the prior art are as follows: the existing method for measuring volatile phenol and cyanide in water quality, soil or municipal sludge is complex and long in time consumption, and is extremely easy to cause harm to the health of measuring personnel.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a method for measuring volatile phenol and cyanide in water quality, soil or municipal sludge.

The invention is realized by the method for measuring the volatile phenol and the cyanide in the water quality, the soil or the municipal sludge, and the method for measuring the volatile phenol and the cyanide in the water quality, the soil or the municipal sludge comprises the following steps:

step one, preparing a volatile phenol solution: mixing the volatile phenol standard solution with the concentration of 1000mg/L with 0.025mol/L sodium hydroxide solution, and diluting to obtain a volatile phenol solution with the concentration of 1 mg/L.

Step two, preparing a cyanide solution: a cyanide standard solution having a concentration of 50mg/L was mixed with a sodium hydroxide solution of 0.025mol/L and diluted to a cyanide solution having a concentration of 2 mg/L.

Step three, determining the concentration of a volatile phenol standard curve: and (3) sucking the prepared volatile phenol solution into a constant volume bottle, and performing constant volume by using distilled water to obtain different standard curve concentrations of the volatile phenol.

Step four, determining the concentration of a cyanide standard curve: and (3) sucking the prepared cyanide solution into a constant volume bottle, and performing constant volume by using distilled water to obtain different standard curve concentrations of the cyanide.

Step five, treating water quality, soil or municipal sludge: taking a sample of water quality soil or municipal sludge to be detected; and (2) placing the soil or the municipal sludge into distilled water, uniformly stirring the soil or the municipal sludge by a stirring device, and placing the mixture into an ultrasonic instrument for ultrasonic treatment to obtain a mixed solution.

Step six, preparing a sample to be detected: and D, filtering the mixed solution obtained in the fifth step by using a filter membrane, and filtering impurities and turbid substances in the mixed solution to obtain the sample to be detected.

And step seven, respectively measuring volatile phenol and cyanide: and (3) conveying the sample to be detected and the chemical reagent into a continuous flow injection analyzer with a volatile phenol and cyanide analysis module by using a pump, acidifying the sample to be detected by using a distillation reagent, distilling out volatile phenol, collecting, and determining the sample to be detected.

Step eight, analyzing a sample to be detected: activating the flow injection analysis device, and setting the time relay to be in a mode of manually turning on and powering off after being powered on for 20-60 s; adjusting a base line, selecting a gain value after stabilization, then converting the analyzer into a sample introduction state, filling a sample introduction ring with a standard sample or a sample by driving of a first low-pressure pump, and then converting the analyzer into an analysis state to analyze a sample to be detected.

And step nine, in the flow injection analysis process, manually turning on a power supply of the time relay, controlling the second electromagnetic valve to be communicated with the waste liquid container to input the reaction liquid output by the reactor into the waste liquid container, and simultaneously controlling an air inlet of the first electromagnetic valve to be communicated with the atmosphere to input air into the optical flow cell.

Step ten, obtaining a linear curve: dividing a sample to be detected into two equal parts, putting the first part into a medium with the pH value of 10.0 +/-0.2, and carrying out online distillation to obtain distillate.

Step eleven, mixing the distillate obtained by the first part of on-line distillation with a continuously flowing 4-aminoantipyrine solution and a potassium ferricyanide solution, carrying out oxidation color development to form yellow antipyrine dye, and carrying out colorimetric determination at the wavelength of 510nm by using a colorimeter.

Step twelve, reacting the second part of samples with chloramine T under the condition that the pH value is less than 8 to form cyanogen chloride-CNCl, reacting the cyanogen chloride with an isonicotinic acid-barbituric acid reagent to form a violet blue dye, carrying out colorimetric determination by a colorimeter at the wavelength of 600nm, and respectively obtaining a linear regression equation.

Furthermore, in the third step, the concentrations of the standard curves of the different volatile phenols are respectively 0, 0.002, 0.004, 0.008, 0.012, 0.020, 0.030 and 0.040.

Further, in the fourth step, the standard curve concentrations of the different cyanides are 0, 0.004, 0.008, 0.016, 0.024, 0.032, 0.040 and 0.060, respectively.

Further, in the fifth step, the ultrasonic treatment conditions are as follows: the ultrasonic frequency is 1.7-2.4 MHz, and the ultrasonic time is 10-20 min.

Further, in the sixth step, the method for filtering the mixed solution comprises: and filtering the mixed solution by using a filter membrane with the thickness of 0.30-0.50 nm for 2-3 times.

Further, in the seventh step, the method for measuring the sample to be measured is as follows:

(1) sending a sample to be tested into a continuous flow injection analyzer with a volatile phenol and cyanide analysis module;

(2) sequentially opening a circulating water cooling machine, a flow injection analyzer host and a sample injector;

(3) opening the peristaltic pump when the temperature of the distiller rises to 100 ℃; and (6) carrying out the determination of the sample to be detected.

Further, in the seventh step, when the volatile phenol and the cyanide are respectively measured, the volatile phenol and the cyanide are respectively measured for 8-10 times.

Further, in the seventh step, the distillation reagent is a phosphoric acid solution, and the preparation method comprises: 30ml of phosphoric acid with the density of 1.65g/ml is added into 50ml of distilled water, and the volume is increased to 200ml by adding the distilled water.

Further, in the eighth step, the analysis method of the sample to be tested is a flow injection analysis method.

Further, in the twelfth step, the method for obtaining the linear regression equation includes:

calculating the content of the sample according to the peak area of the sample to be measured and a standard curve, wherein the calculation formula is as follows:

Y＝a+bX；

wherein, Y is the peak area of sample determination; x is the content of the sample and the unit is mu g/L; a is a standard curve intercept; b is the standard curve slope.

By combining all the technical schemes, the invention has the advantages and positive effects that: the method for measuring the volatile phenol and the cyanide can accurately measure the content of the volatile phenol and the cyanide in water, soil, municipal sludge and other substances, realize the detection of high-toxicity and highly-toxic substances and avoid the damage to human bodies; the determination method is simple to operate and easy to realize, the treatment of the sample to be detected is more convenient, and the accuracy of detection is better; and a standard curve is drawn in the determination, so that the subsequent detection is convenient.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments of the present application will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings can be obtained from the drawings without creative efforts.

FIG. 1 is a flow chart of a method for measuring volatile phenols and cyanides in water quality, soil or municipal sludge according to an embodiment of the invention.

FIG. 2 is a flow chart of a method for separately preparing a volatile phenol solution and a cyanide solution according to an embodiment of the present invention.

FIG. 3 is a flowchart of a method for determining a sample to be tested according to an embodiment of the present invention.

Fig. 4 is a flowchart of a method for analyzing a sample to be tested according to an embodiment of the present invention.

FIG. 5 is a flowchart of a method for measuring absorbance of a volatile phenol solution and a cyanide solution, respectively, according to an embodiment of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Aiming at the problems in the prior art, the invention provides a method for measuring volatile phenol and cyanide in water quality, soil or municipal sludge, and the invention is described in detail below with reference to the accompanying drawings.

As shown in fig. 1, the method for measuring volatile phenols and cyanides in water quality, soil or municipal sludge provided by the embodiment of the invention comprises the following steps:

s101, preparing a volatile phenol solution and a cyanide solution respectively.

S102, determining the concentration of a volatile phenol standard curve: and (3) sucking the prepared volatile phenol solution into a constant volume bottle, and performing constant volume by using distilled water to obtain different standard curve concentrations of the volatile phenol.

S103, carrying out cyanide standard curve concentration determination: and (3) sucking the prepared cyanide solution into a constant volume bottle, and performing constant volume by using distilled water to obtain different standard curve concentrations of the cyanide.

S104, treating water quality, soil or municipal sludge: taking a sample of water quality soil or municipal sludge to be detected; and (2) placing the soil or the municipal sludge into distilled water, uniformly stirring the soil or the municipal sludge by a stirring device, and placing the mixture into an ultrasonic instrument for ultrasonic treatment to obtain a mixed solution.

S105, preparing a sample to be detected: and (4) filtering the mixed solution obtained in the step (S104) by using a filter membrane, and filtering out impurities and turbid substances in the mixed solution to obtain a sample to be detected.

S106, respectively measuring volatile phenol and cyanide: and (3) conveying the sample to be detected and the chemical reagent into a continuous flow injection analyzer with a volatile phenol and cyanide analysis module by using a pump, acidifying the sample to be detected by using a distillation reagent, distilling out volatile phenol, collecting, and determining the sample to be detected.

S107, analyzing a sample to be detected: activating the flow injection analysis device, adjusting the baseline, selecting the gain value after stabilization, and analyzing the sample to be tested.

S108, linear curve acquisition: and (4) respectively measuring the absorbance of the volatile phenol solution and the cyanide solution, and respectively obtaining a linear regression equation.

As shown in fig. 2, in step S101 provided in the embodiment of the present invention, the method for separately preparing the volatile phenol solution and the cyanide solution includes:

s201, preparing a volatile phenol solution: mixing the volatile phenol standard solution with the concentration of 1000mg/L with 0.025mol/L sodium hydroxide solution, and diluting to obtain a volatile phenol solution with the concentration of 1 mg/L.

S202, preparing a cyanide solution: a cyanide standard solution having a concentration of 50mg/L was mixed with a sodium hydroxide solution of 0.025mol/L and diluted to a cyanide solution having a concentration of 2 mg/L.

In step S102 provided in the embodiment of the present invention, the concentrations of the standard curves of the different volatile phenols are 0, 0.002, 0.004, 0.008, 0.012, 0.020, 0.030, and 0.040, respectively.

In step S103 provided in the embodiment of the present invention, the standard curve concentrations of the different cyanides are 0, 0.004, 0.008, 0.016, 0.024, 0.032, 0.040, and 0.060, respectively.

In step S104 provided in the embodiment of the present invention, the ultrasonic processing conditions are as follows: the ultrasonic frequency is 1.7-2.4 MHz, and the ultrasonic time is 10-20 min.

In step S105 provided in the embodiment of the present invention, the method for filtering the mixed solution includes: and filtering the mixed solution by using a filter membrane with the thickness of 0.30-0.50 nm for 2-3 times.

In step S106 provided in the embodiment of the present invention, the distillation reagent is a phosphoric acid solution, and the preparation method includes: 30ml of phosphoric acid with the density of 1.65g/ml is added into 50ml of distilled water, and the volume is increased to 200ml by adding the distilled water.

As shown in fig. 3, in step S106 provided in the embodiment of the present invention, the method for determining the sample to be measured includes:

s301, sending the sample to be tested into a continuous flow injection analyzer with a volatile phenol and cyanide analysis module.

And S302, sequentially opening the circulating cooling water machine, the flow injection analyzer host and the sample injector.

S303, opening a peristaltic pump when the temperature of the distiller rises to 100 ℃; and (6) carrying out the determination of the sample to be detected.

In step S106 provided in the embodiment of the present invention, when the volatile phenol and the cyanide are measured separately, the volatile phenol and the cyanide are measured separately for 8 to 10 times.

In step S107 provided in the embodiment of the present invention, the analysis method of the sample to be detected is a flow injection analysis method.

As shown in fig. 4, in step S107 provided in the embodiment of the present invention, the method for analyzing the sample to be tested includes:

s401, activating the flow injection analysis device, and setting the time relay to be in a mode of manually turning on power and turning off power after the power is turned on for 20-60S.

S402, adjusting the base line, selecting a gain value after stabilization, then converting the analyzer to a sample introduction state, filling the sample introduction ring with a standard sample or a sample by driving of a first low-pressure pump, and then converting the analyzer to an analysis state to analyze the sample to be detected.

And S403, in the flow injection analysis process, manually turning on a power supply of the time relay, controlling the second electromagnetic valve to be communicated with the waste liquid container to input the reaction liquid output by the reactor into the waste liquid container, and simultaneously controlling an air inlet of the first electromagnetic valve to be communicated with the atmosphere to input air into the optical flow cell.

As shown in fig. 5, in step S108 provided in the embodiment of the present invention, the method for separately measuring the absorbance of the volatile phenol solution and the cyanide solution includes the following steps:

and S501, dividing the sample to be detected into two equal parts, putting the first part into a medium with the pH value of 10.0 +/-0.2, and carrying out online distillation.

S502, mixing the first part of distillate with continuously flowing 4-aminoantipyrine and potassium ferricyanide, oxidizing and developing to form yellow antipyrine dye, and carrying out colorimetric determination at the wavelength of 510 nm.

S503, reacting the second part of sample with chloramine T under the condition that the pH value is less than 8 to form cyanogen chloride-CNCl, reacting the cyanogen chloride with an isonicotinic acid-barbituric acid reagent to form a violet blue dye, and carrying out colorimetric determination at the wavelength of 600 nm.

In step S108 provided in the embodiment of the present invention, the method for obtaining the linear regression equation includes:

calculating the content of the sample according to the peak area of the sample to be measured and a standard curve, wherein the calculation formula is as follows:

Y＝a+bX；

wherein, Y is the peak area of sample determination; x is the content of the sample and the unit is mu g/L; a is a standard curve intercept; b is the standard curve slope.

The technical solution of the present invention is further described with reference to the following specific examples.

The embodiment of the invention provides the following steps of measuring volatile phenol and cyanide in city drinking tap water:

respectively preparing volatile phenol solution and cyanide solution; sucking the prepared volatile phenol solution into a constant volume bottle, and performing constant volume by using distilled water to obtain different standard curve concentrations of volatile phenol; sucking the prepared cyanide solution into a constant volume bottle, and performing constant volume by using distilled water to obtain different standard curve concentrations of cyanide;

filtering city drinking tap water, and filtering impurities and turbid substances in the mixed solution to obtain a sample to be detected;

sending the sample to be tested into a continuous flow injection analyzer with a volatile phenol and cyanide analysis module to test the sample to be tested; activating an analysis method, adjusting a base line, selecting a gain value after stabilization, and analyzing a sample to be detected; and (4) respectively measuring the absorbance of the volatile phenol solution and the cyanide solution, and respectively obtaining a linear regression equation. The volatile phenol content and recovery rate in city tap water are shown in table 1; the cyanide content and recovery in city tap water are shown in table 2.

TABLE 1 content and recovery of volatile phenol in city drinking tap water

TABLE 2 cyanide content and recovery in city tap water

The above description is only for the purpose of illustrating the preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made by those skilled in the art within the technical scope of the present invention disclosed herein, which is within the spirit and principle of the present invention, should be covered by the present invention.